EP0110432B1 - Verfahren zur Herstellung von Fluoren-9-carbonsäure - Google Patents
Verfahren zur Herstellung von Fluoren-9-carbonsäure Download PDFInfo
- Publication number
- EP0110432B1 EP0110432B1 EP83201265A EP83201265A EP0110432B1 EP 0110432 B1 EP0110432 B1 EP 0110432B1 EP 83201265 A EP83201265 A EP 83201265A EP 83201265 A EP83201265 A EP 83201265A EP 0110432 B1 EP0110432 B1 EP 0110432B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluorene
- carboxylic acid
- dialkyl carbonate
- potassium
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- DNVJGJUGFFYUPT-UHFFFAOYSA-N 9h-fluorene-9-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)C3=CC=CC=C3C2=C1 DNVJGJUGFFYUPT-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 0 *C1c(cccc2)c2-c2c1cccc2 Chemical compound *C1c(cccc2)c2-c2c1cccc2 0.000 description 1
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 239000003416 antiarrhythmic agent Substances 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- HMOHOVASWYMMHA-UHFFFAOYSA-L barium(2+);diphenoxide Chemical compound [Ba+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 HMOHOVASWYMMHA-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JMPVESVJOFYWTB-UHFFFAOYSA-N dipropan-2-yl carbonate Chemical compound CC(C)OC(=O)OC(C)C JMPVESVJOFYWTB-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GUWHRJQTTVADPB-UHFFFAOYSA-N lithium azide Chemical compound [Li+].[N-]=[N+]=[N-] GUWHRJQTTVADPB-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002912 oxalic acid derivatives Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Definitions
- the invention relates to a process for the preparation of fluorene-9-carboxylic acid from fluorene.
- Fluorene-9-carboxylic acid is an important intermediate in the manufacture of certain anti-diabetic or anti-arrhythmic agents.
- the solution is achieved by reacting fluorene with dialkyl carbonate and alkali hydride or potassium alcoholate, neutralizing the reaction mixture with an acid and isolating the resulting fluorene-9-carboxylic acid ester and then saponifying it.
- the fluorene used as the starting point is contained in the hard coal high temperature tar on average to about 2%. It is technically by redistillation of the coal tar washing oil or direct removal of a fluorene fraction in the primary distillation of the coal tar and subsequent recrystallization, e.g. B. from solution benzene, possibly after removal of phenols and bases.
- a technical product with a purity of approximately 95% can be used for fluorene.
- Potassium or sodium hydride can equally be used as the alkali hydride.
- the amount of alkali hydride used must at least correspond to the stoichiometrically necessary amount. It has been found that the reaction proceeds in a particularly good yield when alkali metal hydride is added in a molar excess.
- Potassium alcoholates which can be used according to the invention are the potassium salts of all lower alcohols, such as methanol, ethanol, propanol, isopropanol, butanol and all isomers, and also amyl alcohol and all isomers. It is essential that the alcoholates contain no free alcohol. The potassium alcoholates are also used at least in the necessary stoichiometric amount, the yield being improved here too by an excess.
- dialkyl carbonate a pure product can be used, such as. B. dimethyl, diethyl, dipropyl or diisopropyl carbonate, the corresponding fluorene-9-carboxylic acid esters. Since these esters are then saponified, mixtures of various dialkyl carbonates or mixed carbonates such as ethyl methyl carbonate or ethyl propyl carbonate can also be used.
- the dialkyl carbonate used advantageously serves both as a reactant and as a solvent for the fluorene. This means that there is always an excess of dialkyl carbonate.
- the amount of dialkyl carbonate added must be at least the stoichiometrically necessary amount.
- an economic yield was only achieved with a more than four-fold stoichiometric excess of the dialkyl carbonate. With more than fifteen times stoichiometry Because of the large amount of solvent, the reaction becomes uneconomical.
- the process is carried out by suspending sodium hydride in an aromatic solvent and / or dialkyl carbonate and slowly adding a solution of fluorene in dialkyl carbonate.
- the reaction takes place with stirring at a temperature in the range of 40-80 ° C for 2-8 hours.
- the mixture is then cooled and the reaction mixture is neutralized with cooling using an acid, advantageously an aqueous solution of a strong inorganic acid.
- Any impurities are then filtered off, the aqueous phase is separated off and the solvent or solvent mixture is separated off from the remaining organic phase by distillation.
- the fluorene-9-carboxylic acid ester remaining in the distillation residue is then acidified.
- the fluorene-9-carboxylic acid precipitates in the form of light beige crystals and is separated off, washed and dried.
- the reaction mixture is carefully allowed to flow into a solution of 400 g (4 mol) of hydrochloric acid, conc., And 500 g of water with water cooling, so that the temperature does not rise above 40.degree.
- the mixture is filtered off from impurities, the water layer is separated off and the solvent is distilled off from the diethyl carbonate layer under reduced pressure. -1700 ml of diethyl carbonate are obtained as the distillate.
- 420 g of hydrochloric acid, 10% are added to the distillation residue and the mixture is heated under reflux for 4 hours. After ⁇ 1/2 hour, the fluorocarboxylic acid fall out at the boiling point crystals.
- reaction mixture is cooled to -20 ° C.
- the precipitated crystalline product is filtered off, washed with 600 ml of toluene and finally with about 500 ml of water free of chloride.
- the wet product obtained (360-400 g) is dried at -80 ° C.
- the yield is 80.7% of theory, based on the fluorene used.
- the yield is 82.7% of theory, based on the fluorene used.
- reaction mixture is carefully allowed to flow into a solution of 220 g (2.2 mol) of hydrochloric acid and 500 g of water with cooling so that the temperature does not rise above 40.degree. Further processing is carried out analogously to Example 1.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3243981 | 1982-11-27 | ||
| DE19823243981 DE3243981A1 (de) | 1982-11-27 | 1982-11-27 | Verfahren zur herstellung von fluoren-9-carbonsaeure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0110432A1 EP0110432A1 (de) | 1984-06-13 |
| EP0110432B1 true EP0110432B1 (de) | 1985-12-04 |
Family
ID=6179240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83201265A Expired EP0110432B1 (de) | 1982-11-27 | 1983-09-02 | Verfahren zur Herstellung von Fluoren-9-carbonsäure |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4564700A (cs) |
| EP (1) | EP0110432B1 (cs) |
| JP (1) | JPS59101437A (cs) |
| DE (2) | DE3243981A1 (cs) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2618767B2 (ja) * | 1991-05-17 | 1997-06-11 | 東海ゴム工業株式会社 | ステアリングカップリング |
| KR960005902B1 (ko) * | 1991-12-30 | 1996-05-03 | 현대자동차주식회사 | 자동차의 후륜 현가장치 |
| US5246248A (en) * | 1992-05-15 | 1993-09-21 | General Motors Corporation | Vehicle rear suspension apparatus |
| JP5124111B2 (ja) * | 2006-07-31 | 2013-01-23 | 大阪瓦斯株式会社 | 膜形成用材料 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2376837A (en) * | 1941-01-13 | 1945-05-22 | Mallinekrodt Chemical Works | Carbalkoxylation of organic compounds |
| US2367632A (en) * | 1942-07-30 | 1945-01-16 | Mallinckrodt Chemical Works | Carbalkoxylation of organic compounds |
| CH286853A (de) * | 1949-04-11 | 1952-11-15 | Thomas Arnold Richard | Verfahren zur Herstellung von 9-Allyl-fluoren-9-carbonsäure. |
| GB969024A (en) * | 1961-04-27 | 1964-09-09 | Koninklijke Pharma Fab Nv | Dihydrodibenzocycloheptene carboxylic acid esters |
| US3369044A (en) * | 1962-07-23 | 1968-02-13 | Geigy Chem Corp | 5-carboxylic acid halide derivatives of 10, 11-dihydro-5h-dibenzo[a, d]cycloheptene |
| US3598564A (en) * | 1962-09-22 | 1971-08-10 | Merck Ag E | Plant growth regulating agents |
| US3636080A (en) * | 1967-02-27 | 1972-01-18 | Hoffmann La Roche | Substituted phenylmalonic acid and phenylalkyl malonic acid esters |
| US3692826A (en) * | 1968-12-18 | 1972-09-19 | Edwin L Patmore | Carboxylation of fluorene |
| US3718690A (en) * | 1971-12-30 | 1973-02-27 | Sun Oil Co | Formation of naphthalene-2,6-dicarboxylic acid |
| JPS573663A (en) * | 1980-06-10 | 1982-01-09 | Namihiko Ogasawara | Coin type game machine |
-
1982
- 1982-11-27 DE DE19823243981 patent/DE3243981A1/de not_active Withdrawn
-
1983
- 1983-09-02 EP EP83201265A patent/EP0110432B1/de not_active Expired
- 1983-09-02 DE DE8383201265T patent/DE3361432D1/de not_active Expired
- 1983-10-21 JP JP58196301A patent/JPS59101437A/ja active Granted
- 1983-11-16 US US06/552,459 patent/US4564700A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3243981A1 (de) | 1984-05-30 |
| JPS59101437A (ja) | 1984-06-12 |
| JPH0419216B2 (cs) | 1992-03-30 |
| DE3361432D1 (en) | 1986-01-16 |
| EP0110432A1 (de) | 1984-06-13 |
| US4564700A (en) | 1986-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2441878B2 (de) | Verfahren zur herstellung von phosphon- und phosphinsaeuren | |
| DE1938513B1 (de) | Verfahren zur Herstellung von D-threo-1-p-Methylsulfonyl-phenyl-2-dichloracetamido-propan-1,3-diol | |
| EP0110432B1 (de) | Verfahren zur Herstellung von Fluoren-9-carbonsäure | |
| DE2607294A1 (de) | Verfahren zur herstellung von 2-amino-1-butanol | |
| DE69029754T2 (de) | Herstellung von Thiophen-2,5-Dicarbonsäurediestern und Tetrahydrothiophen-2,5-dicarbonsäurediestern | |
| DE2636423B1 (de) | Verfahren zur Herstellung von Anthranilsaeureestern | |
| EP0087585A1 (de) | Verfahren zur Herstellung von 3-Alkoxi-acrylnitrilen | |
| DE2410782C2 (de) | Phenylendiessigsäuredialkylester und Verfahren zu deren Herstellung | |
| DE69304634T2 (de) | Verfahren zur Herstellung von N,O-Dialkylhydroxycarbaminsäureestern | |
| EP0537534B1 (de) | Verfahren zur Herstellung von N-(Hydroxyalkyl)-carbamidsäure- alkylestern | |
| DE2721265C2 (de) | Verfahren zur Herstellung von Di- n-propylacetonitril | |
| DE2715933A1 (de) | Verfahren zur herstellung von phosphorylierten amidinen | |
| DE2828011A1 (de) | Verfahren zur herstellung von mandelsaeureestern | |
| EP0018540B1 (de) | Ester des Isocamphyl-guajakols, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von 3-(Iso-camphyl-(5))-cyclohexanol | |
| DD233373A5 (de) | Verfahren zur herstellung von imidazolidinderivaten | |
| DE1244797B (de) | Verfahren zur Herstellung von Phenylestern carbocyclischer, aromatischer, gegebenenfalls kernsubstituierter Mono- und Polycarbonsaeuren | |
| DE2345788A1 (de) | Verfahren zur herstellung eines alkylhalogennitrobenzoats in verbesserter ausbeute | |
| EP0224057B1 (de) | Verfahren zur Herstellung von Isoxazolidin-3-onen | |
| DE1938513C (de) | Verfahren zur Herstellung von D threo 1 p Methylsulfonyl phenyl 2 dichloracetami do propan 1,3 diol | |
| EP0122479A1 (de) | 3-Chlor-1,1-dialkoxyacetone und Verfahren zu ihrer Herstellung | |
| EP0230224B1 (de) | Verfahren zur Herstellung von Alkoxycarbonylisocyanaten | |
| DE1924535C3 (de) | Verfahren zur Herstellung von Esterisocyanaten | |
| DE2145660A1 (de) | Verfahren zur herstellung von acetondicarbonsaeureestern | |
| EP0012868A1 (de) | 1,2,3-Thiadiazol-5-yl-thioglycolsäure, deren Derivate sowie Verfahren zu deren Herstellung | |
| CH654293A5 (de) | Verfahren zur herstellung von p-orsellinsaeureestern. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19840409 |
|
| AK | Designated contracting states |
Designated state(s): CH DE FR GB IT LI |
|
| ITCL | It: translation for ep claims filed |
Representative=s name: BARZANO' E ZANARDO ROMA S.P.A. |
|
| EL | Fr: translation of claims filed | ||
| ITF | It: translation for a ep patent filed | ||
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): CH DE FR GB IT LI |
|
| REF | Corresponds to: |
Ref document number: 3361432 Country of ref document: DE Date of ref document: 19860116 |
|
| ET | Fr: translation filed | ||
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19930824 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19930909 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19930915 Year of fee payment: 11 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19940902 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19940930 Ref country code: CH Effective date: 19940930 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19940902 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19950531 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20000925 Year of fee payment: 18 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020501 |